Bodiuzzaman Mohammad, Murugesan Kathiravan, Yuan Peng, Maity Bholanath, Sagadevan Arunachalam, Malenahalli H Naveen, Wang Song, Maity Partha, Alotaibi Mohammed F, Jiang De-En, Abulikemu Mutalifu, Mohammed Omar F, Cavallo Luigi, Rueping Magnus, Bakr Osman M
Center for Renewable Energy and Storage Technologies (CREST), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
J Am Chem Soc. 2024 Oct 2;146(39):26994-27005. doi: 10.1021/jacs.4c08688. Epub 2024 Sep 19.
Copper nanoclusters (Cu NCs) characterized by their well-defined electronic and optical properties are an ideal platform for organic photocatalysis and exploring atomic-level behaviors. However, their potential as greener, efficient catalysts for challenging reactions like decarboxylative oxygenation under mild conditions remains unexplored. Herein, we present Cu(Nap)(PPh)H (hereafter CuNap), protected by 1-naphthalene thiolate (Nap), which performs well in decarboxylative oxidation (90% yield) under photochemical conditions. In comparison, the isostructural Cu(DCBT)(PPh)H (hereafter CuDCBT), stabilized by 2,4-dichlorobenzenethiolate (DCBT), yields only 28%, and other previously reported Cu NCs (Cu, Cu, Cu, Cu, and Cu) yield in the range of 6-18%. The introduction of naphthalene thiolate to the surface of Cu NCs influences their electronic structure and charge transfer in the ligand shell, enhancing visible light absorption and catalytic performance. Density functional theory (DFT) and experimental evidence suggest that the reaction proceeds primarily through an energy transfer mechanism. The energy transfer pathway is uncommon in the context of previous reports for decarboxylative oxidation reactions. Our findings suggest that strategically manipulating ligands holds significant potential for creating composite active sites on atomically precise copper NCs, resulting in enhanced catalytic efficacy and selectivity across various challenging reactions.
具有明确电子和光学性质的铜纳米团簇（Cu NCs）是有机光催化和探索原子级行为的理想平台。然而，它们作为更绿色、高效的催化剂在温和条件下用于脱羧氧化等具有挑战性的反应的潜力仍未得到探索。在此，我们展示了由1-萘硫醇盐（Nap）保护的Cu(Nap)(PPh)H（以下简称CuNap），其在光化学条件下的脱羧氧化反应中表现出色（产率90%）。相比之下，由2,4-二氯苯硫醇盐（DCBT）稳定的同结构Cu(DCBT)(PPh)H（以下简称CuDCBT）产率仅为28%，其他先前报道的Cu NCs（Cu、Cu、Cu、Cu和Cu）产率在6 - 18%范围内。将萘硫醇盐引入Cu NCs表面会影响其电子结构和配体壳层中的电荷转移，增强可见光吸收和催化性能。密度泛函理论（DFT）和实验证据表明该反应主要通过能量转移机制进行。在先前关于脱羧氧化反应的报道中，这种能量转移途径并不常见。我们的研究结果表明，策略性地操纵配体对于在原子精确的铜纳米团簇上创建复合活性位点具有巨大潜力，从而在各种具有挑战性的反应中提高催化效率和选择性。
